EP0627483B1 - Mindestens eine, alkoxylierte Imidazo-Oxazol Verbindung enthaltende Treibstoffzusätzeformulierung - Google Patents

Mindestens eine, alkoxylierte Imidazo-Oxazol Verbindung enthaltende Treibstoffzusätzeformulierung Download PDF

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EP0627483B1
EP0627483B1 EP94401159A EP94401159A EP0627483B1 EP 0627483 B1 EP0627483 B1 EP 0627483B1 EP 94401159 A EP94401159 A EP 94401159A EP 94401159 A EP94401159 A EP 94401159A EP 0627483 B1 EP0627483 B1 EP 0627483B1
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Prior art keywords
carbon atoms
whole number
hydrogen atom
hydrocarbon group
group containing
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French (fr)
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EP0627483A1 (de
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Henri Delhomme
Jean Gaillard
Philippe Mulard
Danièle Eber
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Elf Antar France
IFP Energies Nouvelles IFPEN
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Elf Antar France
IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C10L1/233—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • the present invention relates to additive formulations, in particular for fuels, comprising at least one alkoxylated imidazo-oxazole compound, at least one compound chosen from the group formed by detergent-dispersants and at least one product chosen from the group formed by mineral lubricating oils or synthetic and polyglycols soluble in said fuel.
  • These formulations are usable as multifunctional additives for fuels used in internal combustion engines and in particular for those used in engines with controlled ignition.
  • the accumulation of these deposits in the combustion chambers can lead to a reduction in the volume of the combustion zone which then results in a increased engine compression ratio. This phenomenon also promotes the appearance of rattling.
  • the deposits that form in the various engine parts in contact with fuel can partially absorb a part of this fuel thus contributing to a modification of the oxidizer-fuel mixture with a fuel depletion phase during absorption and an enrichment phase in the event of a desorption of this fuel. The modification of the richness of the fuel-air mixture no longer allows the engine to work in optimal conditions.
  • the accumulation of deposits in the engines and in particular on the valves intake can also be reduced by the use of fuels containing certain additives, for example additives of the detergent type which may be combined for example with anti-corrosion or anti-deposit additives for combustion chamber.
  • additives of the detergent type which may be combined for example with anti-corrosion or anti-deposit additives for combustion chamber.
  • Additives well known in the trade, for example those of the polyisobutene-amine type, are usually combined with a mineral or synthetic oil and are likely to cause increased fouling of the combustion chambers and therefore an increase in the octane requirement of the engine with greater sensitivity to rattling phenomenon.
  • Contamination of the combustion chambers occurs gradually during engine operation.
  • the latter is characterized by its octane requirement which corresponds to the minimum octane number of fuel required for the engine in order to operate without rattling.
  • the value of the engine octane requirement exceeds, in particular as a result of fouling of the combustion chambers, the value of the octane number of the fuel used to power this engine, we observe the rattling phenomenon.
  • the increased octane requirement of the engine constitutes conventionally, for those skilled in the art, the ORI phenomenon according to the Anglo-Saxon abbreviation of "Octane Requirement Increase".
  • compositions which can be used in particular in engine fuels.
  • the compositions such as those described for example in patent application EP-A-327 097 have good anti-ORI properties but relatively limited detergent properties. Furthermore, these compositions are not described as having good anticorrosion properties.
  • formulations usable in particular as multifunctional additives for fuels engines in particular for fuels used in ignition engines ordered.
  • the formulations of the present invention have excellent properties detergents on the intake valves and the carburetor or injectors, and have very good anticorrosion properties.
  • formulations according to the present invention can be used in particular as multifunctional additives for fuels and, for example, as additives in fuels used in spark ignition engines in which they allow, in particular, to limit the increase in octane requirement (ORI) of these drivers and therefore to limit, delay or even avoid, the appearance of the phenomenon of rattling.
  • ORI octane requirement
  • the formulations according to the present invention combine this anti-ORI action with detergent action both at the carburetor and at the injectors as well as at the intake valves. Furthermore, these formulations have anticorrosion properties both in the fuels used for engines spark ignition than in those used in spark ignition engines compression (Diesel engine). In addition, these formulations used in fuels used for spark ignition engines avoid, on the one hand, the appearance of the phenomenon of sticking of the intake valves and, on the other hand, does not not contribute to the formation of deposits (black mud) in motor oils providing lubrication.
  • the subject of the present invention is a formulation of additives, in particular for fuels, which comprises at least one constituent (K), at least one constituent (L) and at least one constituent (M), said constituent (K) consisting of at least one heterocyclic compound of imidazo-oxazole type, comprising an alkoxylated side chain, of general formula (I): in which R 1 represents a hydrogen atom or a hydrocarbon group having from 1 to 40 carbon atoms and preferably from 4 to 25 carbon atoms, R 2 represents a hydrogen atom or a hydrocarbon group having from 1 to 12 carbon atoms, often from 1 to 6 carbon atoms and preferably from 1 to 3 carbon atoms, A, B and C, identical or different, each represent a divalent hydrocarbon group having from 2 to 6 carbon atoms and preferably from 2 to 4 carbon atoms, n is an integer from 5 to 50 preferably from 10 to 50 and most often from 10 to 25, m and p, identical or different, are each zero or an integer from 1 to 25, and the
  • These fuels may also contain other additives, such as for example, in particular in the case of the fuels used for spark-ignition engines, anti-knock additives such as compounds lead (e.g. tetraethyl lead), ethers such as methyltertiobutylether or methyltertioamylether or a mixture of methanol and tertiary butyl alcohol and anti-icing additives.
  • anti-knock additives such as compounds lead (e.g. tetraethyl lead), ethers such as methyltertiobutylether or methyltertioamylether or a mixture of methanol and tertiary butyl alcohol and anti-icing additives.
  • the constituent (K) is most often chosen from the compounds of general formula (I) above in which R 1 represents an alkyl, alkenyl, aryl, alkaryl or aralkyl group and preferably an alkyl or alkenyl group, linear or branched , R 2 most often represents a hydrogen atom or alkyl group, linear or branched and preferably linear.
  • the preferred constituents (K), of general formula (I) above, are those in which m and p are equal to zero, in which A represents an alkylene group having from 2 to 4 carbon atoms and R 2 a d atom hydrogen when A represents the dimethylene group of formula -CH 2 -CH 2 - and an alkyl group preferably linear having 2 carbon atoms less than the group A when the latter represents an alkylene group having 3 or 4 carbon atoms .
  • the preferred compounds are those in which A represents the dimethylene group, the methyl-1 dimethylene group or the ethyl-1 dimethylene group which are groups derived respectively from ethylene oxide, from propylene oxide and butene-1 oxide and which have the following formulas:
  • Heterocyclic compounds of imidazo-oxazole type used as component (K) can be manufactured by any methods known to those skilled in the art. As non-limiting examples of methods for preparing these compounds of general formula (I) above we will quote and illustrate in an example which follows the following method.
  • the reaction is carried out, in the presence or in the absence of an inert organic solvent, at a temperature of 90 ° C to 190 ° C and most often from 100 ° C to 140 ° C, in the presence of a basic catalyst, at least one alkylene oxide having from 2 to 6 carbon atoms and preferably from 2 to 4 carbon atoms in its molecule, with at least one unsubstituted or substituted 1- (2-hydroxyethyl) -imidazoline in position 2 by a hydrocarbon group having from 1 to 40 carbon atoms of general formula (II) below: in which R 1 has the definition given above.
  • a basic catalyst at least one alkylene oxide having from 2 to 6 carbon atoms and preferably from 2 to 4 carbon atoms in its molecule, with at least one unsubstituted or substituted 1- (2-hydroxyethyl) -imidazoline in position 2 by a hydrocarbon group having from 1 to 40 carbon atoms of general formula (II) below: in which R 1 has
  • the reaction is usually carried out under a pressure of 1 to 7 bar (1 bar equals 0.1 megapascal).
  • the duration of the reaction is variable depending on the oxide of alkylene employed and also according to the number of moles of alkylene oxide used works for 1 mole of imidazoline. This duration is often from 6 to 24 hours (h) and most often from 7 to 10 hours.
  • the molar ratio imidazoline-alkylene oxide is usually 1: 5 to 1:50 and preferably from 1:10 to 1:50 and most often from 1:10 at 1:25.
  • Usually a basic amount of catalyst is used 0.1 to 0.6 moles per mole of imidazoline.
  • the catalyst is removed in end of reaction either by washing with water or by an ion exchange type treatment with example using a solid ion exchanger.
  • the basic catalyst is usually chosen from the group formed by the methylate sodium, sodium ethylate, potassium tert-butoxide, potash and soda.
  • the alkylene oxide is most often chosen from the group formed by the oxide ethylene, propylene oxide and butene-1 oxide.
  • Imidazolines used to prepare heterocyclic compounds of the type imidazo-oxazoles of the present invention are known compounds and for some of them commercial.
  • Imidazolines of formula (II) are for example described in patent application EP-A-74 724.
  • These imidazolines are most often synthesized by reaction of at least one organic carboxylic acid on N- (2-hydroxyethyl) -ethylenediamine. The reaction proceeds by a first step of amidation followed by cyclization.
  • the organic acids used have usually from 2 to 26 carbon atoms; they are preferably acids aliphatic monocarboxylic.
  • 1- (2-hydroxyethyl) -2-heptadecenyl imidazoline will be used, prepared for example from oleic acid and N- (2-hydroxyethyl) ethylenediamine.
  • This preparation is for example described in the patent US-A-2 987 515.
  • Mention may also be made, for example, of 1- (2-hydroxyethyl) -2-methyl imidazoline prepared for example from acid acetic acid and N- (2-hydroxyethyl-) ethylenediamine.
  • 1- (2-hydroxyethyl) -2 heptadecenylimidazoline is marketed by the company CIBA-GEIGY under the name "Amine-O".
  • the formulations will comprise at least one constituent (L) chosen from the group formed by detergent-dispersant products.
  • This constituent (L) is usually chosen from the group formed by polyolefins, preferably polyisobutenes, polyisobuten-amines, mixtures of these types of compounds and the products which are in particular described in European patent application EP-A -349,369 in the name of the applicant, as well as those described in patent US-A-4,375,974.
  • the products described in application EP-A-349,369 result from the reaction in a first step of at least one derivative succinic chosen from the group formed by alkenylsuccinic acids and anhydrides and polyalkenylsuccinic acids and anhydrides on at least one 1- (2-hydroxy-ethyl-) imidazoline substituted in position 2 by a linear or branched alkyl or alkenyl radical, having from 1 to 25 carbon atoms, the imidazoline / succinic derivative molar ratio being from 0.1: 1 to 0.9: 1, preferably from 0.2: 1 to 0.8: 1 and most often from 0 , 3: 1 to 0.7: 1, said step being eff carried out under conditions such that at least 0.15 mole of water is formed and eliminated per mole of imidazoline used; and in a second stage of the reaction of the product resulting from the first stage with at least one polyamine corresponding to one of the following general formulas: in which R 13 represents a hydrogen atom or a hydrocarbon group having
  • the acid or acid derivative used in the context of the present invention to prepare component (L) is usually a succinic compound or a compound alkyl succinic or alkenyl succinic, preferably a succinic anhydride.
  • succinic anhydride may be mentioned, methylsuccinic anhydride often called citraconic anhydride, and alkylsuccinic or alkenylsuccinic anhydrides usually having a mass number average molecular from 200 to 3,000, preferably 500 to 2,000 and most often 700 to 1,500.
  • succinic derivatives are widely described in prior art; they are for example obtained by the action of at least one alpha olefin or a chlorinated hydrocarbon on maleic acid or anhydride.
  • the alpha olefin or the chlorinated hydrocarbon used in this synthesis can be linear or branched, and usually contain from 10 to 150 carbon atoms, preferably from 15 to 80 carbon atoms and most often 20 to 75 carbon atoms in their molecule.
  • This olefin can also be an oligomer, for example a dimer, a trimer or a tetramer, or a polymer of a lower olefin, for example from 2 to 10 carbon atoms, such as ethylene, propylene, n-butene-1, isobutene, n-hexene-1, n-octene-1, methyl-2-heptene-1 or methyl-2-propyl-5-hexene-1. It is possible to use mixtures of olefins or mixtures of hydrocarbons chlorinated.
  • succinic anhydrides include anhydride n-octadecenylsuccinic, dodecenylsuccinic anhydride and anhydrides polyisobutenyl succinics, often called PIBSA, having a molecular weight number average as defined above.
  • 1- (2-hydroxyethyl -) - imidazolines substituted in position 2 by a radical alkyl or alkenyl having from 1 to 25 carbon atoms used in the context of present invention for preparing component (L), are usually compounds commercial or which can be synthesized for example by reaction of at least one organic acid with N- (2-hydroxy-ethyl) -ethylenediamine. The reaction proceeds as described above and the acids used are those mentioned above in the context of the preparation of the compounds of general formula (I). We will use for example one imidazolines cited above.
  • the first stage of preparation of the constituent (L) is usually carried out by progressive addition of the imidazoline derivative to a solution of the succinic derivative in an organic solvent, at room temperature, then heating to a temperature usually between 65 ° C and 250 ° C and preferably between 80 ° C and 200 ° C.
  • the organic solvent used in this preparation has a boiling point included between 65 ° C and 250 ° C and is usually chosen so as to be able to allow elimination of the water formed during the condensation of imidazoline on the derivative succinic, preferably in the form of a water-organic solvent azeotrope.
  • an organic solvent such as benzene, toluene, xylenes, ethylbenzene or a cut of hydrocarbons such as by example the SOLVESSO 150 commercial cut (190-209 ° C) containing 99% weight of aromatic compounds. It is possible to use mixtures of solvents, for example example a mixture of xylenes.
  • the duration of the heating after the addition of imidazoline is usually 0.5 to 7 hours, preferably 1 to 5 hours. This first step will preferably be continued at the chosen temperature until the end release of water formed during the reaction.
  • the amount of water removed during this first step is usually 0.15 to 0.6 mole and most often about 0.5 mole per mole imidazoline involved in the reaction.
  • To the product or mixture from this first stage after possible cooling, preferably gradually added to the minus one polyamine, preferably diluted in an organic solvent, then usually heated to a temperature between 65 ° C and 250 ° C and preferably between 80 ° C and 200 ° C.
  • the solvent used in the second step is preferably the same as the one in the first step and the temperature is also the same during these two stages. Reactions are usually carried out at a temperature corresponding to the reflux temperature.
  • the duration of this heating during this second stage is usually 0.1 to 7 hours and from preferably 0.2 to 5 hours.
  • the amount of polyamine used is at least 0.1 mole per mole of succinic anhydride introduced during the first stage and it is preferably such that the total amount of substituted imidazoline and polyamine used in the preparation either from 0.8 to 1.2 mole, preferably from 0.9 to 1.1 mole per mole of succinic derivative.
  • the imidazoline substituted molar ratio on polyamine is preferably 1: 1 to 7: 1 and most preferably 1 : 1 to 3: 1.
  • the amount of water removed during this second step is usually such that the amount of total water removed during the two successive reactions represents 0.2 to 0.7 mole per mole of succinic derivative.
  • the polyamines of formula (III) are preferably those in which R 13 is a hydrogen atom or a hydrocarbon group having from 1 to 30 carbon atoms, Z is preferably a group -NR 15 - in which R 15 represents preferably a hydrogen atom or a hydrocarbon group having from 1 to 30 carbon atoms, each of R 14 independently represents preferably a hydrogen atom or a methyl group, a is an integer from 2 to 4 and when Z is a group -NR 15 - b is preferably an integer from 1 to 5.
  • Z is -NR 15 -, R 13 , R 14 and R 15 each represent a hydrogen atom, a is equal to 2 and b is a number integer from 1 to 5 or those in which R 13 represents a hydrocarbon group preferably having from 5 to 24 carbon atoms, Z represents a group -NR 15 - in which R 15 is a hydrogen atom, R 14 represents an atom of hydrogen, a is an integer from 2 to 4, preferably 3, and b is an integer from 1 to 5, preferably 1.
  • the hydrocarbon groups R 13 and R 15 are usually alkyl, alkenyl, linear or branched, aryl, aryl-alkyl (aralkyl), alkyl-aryl (alkaryl) or cycloaliphatic groups.
  • the groups R 13 and R 15 are preferably alkyl or alkenyl groups, linear or branched.
  • the hydrocarbon group R 14 is usually a preferably linear alkyl group, for example methyl, ethyl, n-propyl or n-butyl.
  • the alpha-omega biprimary diamines mentioned below trimethylenediamine, trimethyl-2,2,4 and -2,4,4 hexamethylenediamine
  • N-alkyl diamino-1,3 propane for example the N-dodecyldiamino-1,3 propane, N-tetradecyldiamino-1,3 propane, N-hexadecyldiamino-1,3 propane, N-octadecyldiamino-1,3 propane, N-eicosyldiamino-1,3 propane and N-docosyldiamino-1,3 propane
  • N-alkyldipropylene triamines for example N-hexadecyldipropylene triamine, N-octadecyldipropylene triamine, N-eicosyldipropylene triamine and N-docosyldipropylene
  • etheramines examples include N- (3-octyloxy-propyl) diamino-1,3 propane, N- (3-decyloxy-propyl) 1,3-diamino propane, N- [(2,4,6-trimethyl decyl) 3-oxy propyl] diamino-1,3 propane.
  • the polyamines of formulas (IV) are preferably those in which R 13 and R 15 each represent a hydrogen atom, D, E, F and G, identical or different, each represent an alkylene group having from 2 to 4 atoms carbon for example ethylene, trimethylene, methylethylene, tetramethylene, methyltrimethylene, 1-methyltrimethylene and 2-methyltrimethylene, f is an integer from 1 to 60 and g and h are equal to zero or f is an integer from 1 to 59 , h is zero or an integer such that the sum f + h is from 1 to 59 and g is an integer from 1 to 50, with in each case the sum f + g + h equal to an integer from 1 to 60.
  • biprimary alpha-omega diamines which are compounds well known to those skilled in the art.
  • specific compounds there may be mentioned, by way of nonlimiting example,: ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, hexamethylenediamine) -triamine, 2,2-dimethyl-1,3-propanediamine, N, N'-bis (3-amino-propyl) -ethylenediamine, (2-aminoethyl) -3-amino propylamine, trimethyl-hexamethylenediamines for amines which do not contain oxygen atoms in their formula.
  • amines containing oxygen atoms in their formula mention may be made of the polyamines of formula: NH 2 -R 8 - (- OR 9 -) c - (- OR 10 -) d - (- OR 11 -) e -NH 2 in which preferably R 8 , R 9 R 10 and R 11 , identical or different, each represent an alkylidene group having from 2 to 4 carbon atoms for example ethylidene (dimethylene), propylidene (trimethylene), isopropylidene (1-methyl dimethylene ), butylidene (tetramethylene), isobutylidene (2-methyltrimethylene), preferably c is an integer from 1 to 60 and d and e are equal to zero or c is an integer from 1 to 59, e is zero or one integer such that the sum c + e is from 1 to 59 and d is an integer from 1 to 50, with in each case the sum c + d +
  • component (L) The products described by the applicant in US-A-4,375,974 and usable, in the context of the present invention as component (L) are those resulting from the reaction of at least one polyamine, having at least one amino group primary and corresponding to the general formula (III) above, on at least one derivative succinics such as those described above, said reaction being carried out in conditions for the formation and elimination of the reaction water. Most often the reaction is carried out at a temperature of 120 ° C to 200 ° C with a ratio molar amine on succinic derivative from 0.9: 1 to 1.2: 1. This reaction can be carried out in the absence of solvent or in the presence of a solvent such as for example an aromatic hydrocarbon or a cut of hydrocarbons having a point boiling from 70 ° C to 250 ° C.
  • a solvent such as for example an aromatic hydrocarbon or a cut of hydrocarbons having a point boiling from 70 ° C to 250 ° C.
  • the constituent (L) which can be used in the context of the present invention can also be chosen from the group formed by polyisobutenes, polyisobuten-amines, mixtures of these two types of compounds.
  • the polyolefins used can be polymers or copolymers or the corresponding amino or hydrogenated derivatives formed from hydrocarbons having 2 to 10 carbon atoms in their molecule.
  • polymeric compounds are usually prepared from mono-olefinic compounds or diolefinic and usually have an average molecular weight in number of 500 to 10,000 often from 500 to 3,500 and preferably from 650 to 2,600.
  • the starting compounds used for manufacture these polymers are olefins having 2 to 6 carbon atoms in their molecule, such as for example ethylene, propylene, isopropylene, butene, isobutene, amylene, hexylene, butadiene and isoprene.
  • propylene, isopropylene, butene and isobutene are those obtained by cracking high molecular weight olefin polymers or copolymers having a molecular weight in the molecular weight range mentioned above.
  • polypropylenes of average molecular mass in number of 750 to 1,000 and for example around 800 polyisobutenes of molecular mass number average from 1,000 to 1,500 and for example around 1,300.
  • the constituent (L) is a mixture comprising a majority proportion of polyisobutene-ethylenediamine and a minority proportion of polyisobutene.
  • This mixture is most often employee dissolved in a hydrocarbon solvent so as to facilitate its incorporation in the fuel.
  • the proportion of amino polymer in this mixture is usually 50% to 80% by weight and for example about 60% by weight and the proportion of hydrocarbon polymer is usually from 5% to about 30% by weight and preferably from 10% to 25% by weight.
  • Polyisobutene ethylene diamine is a compound of general formula: in which z is a number from 10 to 40, preferably from 30 to 35 and for example 33.
  • Polyisobutene is a compound of general formula: in which t is a number from 10 to 40, preferably from 30 to 35 and for example 33.
  • the solvent used to dissolve the polymeric compounds and facilitate their incorporation into the fuel is most often a light aromatic distillate.
  • component (L) comprising, dissolved in a light aromatic distillate, a polyisobutene and a polyisobutene-ethylene diamine as described above
  • the product sold by the company CHEVRON CHEMICAL COMPANY under the trade name ORONITE OGA can be used.
  • ORONITE OGA-472 is a composition comprising approximately 60% by weight of polyisobutene-ethylene diamine, approximately 27% by weight of polyisobutene and approximately 13% by weight of light aromatic distillate comprising xylene and C 9 alkylbenzenes.
  • the formulations also contain at least one constituent (M) chosen from the group formed by mineral or synthetic lubricating oils and polyglycols, soluble in said fuel, preferably having a number average molecular weight of 480 to 2,100. and of general formula (VIII): wherein each of the R groups independently represents a hydrocarbon group having 2 to 6 carbon atoms and x represents the average degree of polymerization.
  • M constituent
  • R groups independently represents a hydrocarbon group having 2 to 6 carbon atoms
  • x represents the average degree of polymerization.
  • the constituent (M) is a polyglycol, having a polydispersity index from 1 to 1.25 and preferably from 1 to 1.15, of general formula (VIII) in which each of the R groups independently represents an alkylene group, linear or branched, having 2 to 4 carbon atoms, preferably an ethylene or propylene group.
  • the polyglycol used is preferably a polyglycol of average molecular mass in number from 600 to 1,800 and most often from 650 to 1,250.
  • mineral or synthetic lubricating oils which can be used as constituent (M) there may be mentioned by way of nonlimiting examples for oils mineral, lubricating oils known to those skilled in the art as denominations 500 NS and 600 NS, and for synthetic lubricating oils the polyol ethers and esters and in particular polyoxyalkylene glycol ethers.
  • the formulations according to the invention are in particular usable as an additive having good anti-corrosion activity for a fuel based on hydrocarbons or a mixture of hydrocarbons and at least one oxygenated compound chosen from the group formed by alcohols and ethers.
  • These formulations can also be used as an additive.
  • multifunctional having in particular good anti-ORI and detergent-dispersant properties for engine fuel, for positive ignition engine, based of hydrocarbons or of a mixture of hydrocarbons and at least one oxygenated compound chosen from the group formed by alcohols and ethers.
  • these formulations are added to the fuel so as to obtain a concentration of mass, of the additive composition in the engine fuel, from 10 to 10,000 ppm, often from 100 to 5,000 ppm and preferably from 100 to 2,000 ppm.
  • the weight ratio of the constituent (K) to constituent (L) [(K) / (L)] is usually 0.02: 1 to 4: 1.
  • This ratio is often from 0.02: 1 to 2: 1 and preferably from 0.1: 1 to 2: 1.
  • the weight ratio of component (L) to component (M) [(L) / (M)] is usually 0.05: 1 to 10: 1. This ratio is often 0.05: 1 to 5: 1 and preferably 0.01: 1 to 2: 1.
  • the invention also relates to heterocyclic compounds of imidazo-oxazole type. alkoxylated themselves, having the formula (I), as described above.
  • the product obtained is transferred to an Erlenmeyer flask topped with a condenser and then diluted with 300 ml of toluene. After adding 89 g of Ambosol 500 resin (trade name of a magnesium acid silicate sold by the company HOECHST), the medium is brought to 75 ° C. for 1 hour with stirring. After filtration and evaporation of the solvent, 563 g (approximately 93% conversion) of the desired final product are obtained. The kinematic viscosity of this product measured at 40 ° C is 1.68 10 -4 m 2 / s. This product is characterized by infrared, mass spectrometry and elementary analysis.
  • the mass spectrum obtained by electronic impact on a magnetic sector device having an electron beam with a power of 70 electron volts presents a fragment of molecular mass 59 of formula: a fragment of molecular mass 117 and a fragment of molecular mass 175 of formula: in which there is respectively 1 and 2 and a fragment of molecular mass 239 of formula:
  • 1,018 g of polyisobutenyl succinic anhydride PIBSA
  • condensation polyisobutene polyisobutene of average molecular mass in number of 920
  • maleic anhydride the assay of the anhydride functions of this product shows that there is 0.7 anhydride function per kilogram
  • 1,018 g of xylene are loaded into a 2 liter reactor with mechanical agitation, a Dean-Stark separator and a temperature control system.
  • the reactor temperature is lowered to 50 ° C. and then maintained at this value during the time of the gradual addition (dropwise) of 56 g (0.297 mole) of tetraethylenepentamine diluted in 49 g of xylene. At the end of this addition the mixture is again brought to reflux for 15 minutes. Water elimination again occurs. The total amount of water collected during these two reaction stages is 7.2 ml.
  • the infrared spectrum shows two absorption bands (1,710 cm -1 and 1,770 cm -1 ) characteristic of the succinimide function with a shoulder (1,740 cm -1 ) characteristic of the ester function.
  • Solutions are prepared, in xylene, of formulations F1 to F7 comprising various weight quantities of the constituents K, L, M defined below.
  • Component K is formed by the product obtained in Example 1.
  • Component L is formed by the composition obtained in Example 2.
  • the formulation F1 according to the present invention contains the constituent K obtained in Example 1, component L and component M described above. These constituents are used in a weight ratio, in terms of active ingredient, K: L: M of 1: 5: 4.
  • the formulation F2 (comparison formulation) contains the constituent L as well as the constituent M described above, but not constituent K.
  • the weight ratio in active ingredient L: M is 1.25: 1.
  • the formulation F3 (comparison formulation) contains the constituent L described above, but no constituent K nor M.
  • the formulation F4 (comparison formulation) contains the constituent M described above, but no constituent K nor L.
  • the formulation F5 (comparison formulation) contains the constituent K as well as the constituent L described above, but not constituent M.
  • the weight ratio in active ingredient K: L is 0.2: 1.
  • the formulation F6 (comparison formulation) contains the constituent K as well as the constituent M described above, but not constituent L.
  • the weight ratio in active ingredient K: M is 0.25: 1.
  • the formulation F7 (comparison formulation) contains the constituent K described above, but no constituent L nor M.
  • the various formulations have been added to the fuel so as to have a active ingredient pea concentration of 600 ppm.
  • the ignition advance values corresponding to the appearance of the phenomenon of rattling, expressed in crankshaft degrees and designated by the initials KLSA (Anglo-Saxon initials of "Knock Limit Spark Advance", are determined successively at 0, 50, 100, 150, 200, 300 and 400 hours for 7 regimes different from the engine: 1,500, 2,000, 2,500, 3,000, 3,500, 4,000 and 4,500 rpm.
  • KLSA Anglo-Saxon initials of "Knock Limit Spark Advance
  • the results obtained are expressed in terms of variations in advance limit to ignition between 0 and 400 hours ( ⁇ KLSA) at different engine speeds and are presented in Table II below. Average weights (expressed in milligrams (mg) per valve) deposits on the intake valves are also mentioned in this table.
  • the “detergency” detergency properties of the fuels containing the formulations prepared in Example 3 are evaluated.
  • the engine test procedure is carried out according to European standard R5-CEC-F03-T-81.
  • the results are expressed in terms of merit from zero to ten.
  • a merit 10 corresponds to a clean carburetor and a merit 0 to a very dirty carburetor.
  • the fuel used in these assessments is an unleaded premium fuel (S2), engine octane rating of 85.8 and research octane rating of 96.4.
  • This premium fuel has an initial distillation point of 35 ° C and an end point of distillation of 204 ° C.
  • each test is usually 60 hours.
  • the engine is conditioned with new valves that are weighed.
  • the valves are removed, washed with hexane, dried, then weighed after disposal physical (by scraping) of deposits formed on the valve on the combustion chamber side.
  • the results presented below give the average of the deposits by weight compared to a valve, calculated from the weight of deposits measured, on the tulip of each intake valve, by difference between the weight of said new valve and the weight of said valve at the end of each test after removal of deposits on the chamber side combustion.
  • each valve is also assessed by visual rating (side admission: tulip) in terms of merit from 1 to 10 according to the procedure usually called CRC (English initials of Coordinating Research Council) by men of career ; the results are expressed below as an average per valve; a merit of 10 corresponds to a clean valve and a merit of 1 to a very clean valve dirty.
  • CRC Coordinating Research Council
  • the fuel used in these assessments is the unleaded premium fuel (S2), the main characteristics were given in example 5 above.
  • the quantity of formulation is added to the fuel so as to obtain a concentration, by weight of active material in the additive fuel, specified for each example in Table V below giving the results obtained: ADDITIVE FUEL ADDITIVE QUANTITY % OF CORROSIVE AREA Fuel only 0 ppm 100 Fuel + Formula F1 600 ppm 0 Fuel + Formula F2 600 ppm 0 Fuel + Formula F3 600 ppm 0 Fuel + Formulation F4 600 ppm 100 Fuel + Formula F5 600 ppm 50 Fuel + Formula F6 600 ppm 100 Fuel + Formula F7 600 ppm 100

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Claims (20)

  1. Zusätzeformulierung, insbesondere für Treibstoffe, dadurch gekennzeichnet, daß sie mindestens eine Komponente (K), mindestens eine Komponente (L) und mindestens eine Komponente (M) beinhalter, wobei die besagte Komponente (K) aus mindestens einer heterocyclischen Verbindung imidazooxazolischer Art besteht, eine alkoxylierte Seitenkette enthält, gemäß der Summenformel (1) :
    Figure 00380001
    in der R1 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 1 bis 40 Kohlenstoffatomen, R2 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 1 bis 12 Kohlenstoffatomen darstellt, wobei A, B, und C identisch oder unterschiedlich sind und jeweils eine zweiwertige teerhaltige Gruppe mit 2 bis 6 Kohlenstoffatomen darstellen, n ist eine ganze Zahl zwischen 5 und 50, m und p - ob identisch oder unterschiedlich - sind je gleich Null oder eine ganze Zahl von 1 bis 25, die Summe n+m+p ist eine ganze Zahl von 5 bis 50, wobei die besagte Komponente (L) aus mindestens einer Verbindung besteht, die in der Gruppe der Detergens-Dispergiermittel gewählt wurde, und die besagte Komponente (M) aus mindestens einer Verbindung besteht, die in der Gruppe der mineralischen oder synthetischen Schmieröle und der in dem besagten Treibstoff löslischen Polyglykole ausgesucht wurde.
  2. Formulierung gemäß Anspruch 1, in der die Komponente (K) unter den Verbindungen nach der Summenformel (I) ausgesucht wird, in der R1 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 4 bis 25 Kohlenstoffatomen, R2 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 1 bis 6 Kohlenstoffatomen darstellt, wobei A, B, und C identisch oder unterschiedlich sind und jeweils eine zweiwertige teerhaltige Gruppe mit 2 bis 4 Kohlenstoffatomen darstellen, n ist eine ganze Zahl zwischen 10 und 50, m und p - ob identisch oder unterschiedlich - sind je gleich Null oder eine ganze Zahl von 1 bis 25, die Summe n+m+p ist eine ganze Zahl von 10 bis 50.
  3. Formulierung gemäß Anspruch 1 oder 2, in der die Komponente (K) unter den Verbindungen nach der Summenformel (I) ausgesucht wird, in der R1 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 4 bis 25 Kohlenstoffatom, R2 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 1 bis 31 Kohlenstoffatomen darstellt, wobei A, B, und C identisch oder unterschiedlich sind und jeweils eine zweiwertige teerhaltige Gruppe mit 2 bis 4 Kohlenstoffatomen darstellen, n ist eine ganze Zahl zwischen 10 und 25, m und p - ob identisch oder unterschiedlich - sind je gleich Null oder eine ganze Zahl von 1 bis 25, die Summe n+m+p ist eine ganze Zahl von 10 bis 25.
  4. Formulierung gemäß einem der Ansprüche 1 bis 3, in der die Komponente (K) unter den Verbindungen nach der Summenformel (I) ausgesucht wird, in der R1 ein Wasserstoffatom oder eine Alkyl-, Alkenyl-, Aryl-, Alkaryl- oder Aralkylgruppierung, R2 ein Wasserstoffatom oder eine Alkylgruppierung, die geradkettig oder verzweigt, vorzugsweise geradkettig, ist, m und p sind gleich Null und A stellt die Dimethylengruppe, die Methyl-1 dimethylen-Gruppe oder die Ethyl-1 dimethylen-Gruppe dar.
  5. Formulierung gemäß einem der Ansprüche 1 bis 4, in der die Komponente (K) unter den Verbindung nach der Summenformel (I) ausgesucht wird, in der R1 ein Wasserstoffatom oder eine Alkyl-, Alkenylgruppierung, die geradkettig oder verzweigt ist, darstellt.
  6. Formulierung gemäß einem der Ansprüche 1 bis 5, in der die Komponente (L), in der Gruppe der Polyolefine, der Polyisobutenamine, der Gemische aus diesen Verbindungsarten, der Produkte aus der Reaktion in einer ersten Stufe von mindestens einem Bernsteinsäurederivat aus der Gruppe der Alkenylbernsteinsäuren und -anhydride und der Polyalkenyl-bernsteinsäuren und -anhydride mit mindestens einem 1-(2-Hydroxy-Ethyl)imidazolin, das in der Position 2 durch ein geradkettiges oder ein verzweigtes Alkyl- oder Alkenylradikal mit 1 bis 25 Kohlenstoffatomen ersetzt wird, ausgesucht wird, wobei das Molverhältnis zwischen dem Imidazolin und dem Bernsteinsäurederivat 0,1 : 1 bis 0,9 : 1 beträgt; die besagte Stufe wird unter solchen Bedingungen durchgeführt, daß mindestens 0,15 Mol Wasser pro Mol des eingesetzten Imidazolins entsteht und entzogen wird; und in einer zweiten Stufe aus der Reaktion des aus der ersten Stufe stammenden Produktes mit mindestens einem Polyamin, das einer der folgenden Summenformeln entspricht:
    Figure 00400001
    Figure 00400002
    in denen R13 ein Wasserstoffatom oder eine teerhaltige Gruppe mit1 bis 60 Kohlenstoffatomen darstellt, Z unter den -O- und -NR15- Gruppen ausgesucht wird, in denen R15 ein Wasserstoffatom oder eine teerhaltige Gruppe mit 1 bis 60 Kohlenstoffatomen ist, wobei R13 und R15 zusammen mit dem Stickstoffatom, an dem sie gebunden sind, eine heterocyclische Verbindung bilden können; jeder einzelne R14 stellt ein Wasserstoffatom oder eine teerhaltige Gruppe mit 1 bis 4 Kohlenstoffatomen dar, a ist eine ganze Zahl von 2 bis 6, b eine ganze Zahl von 1 bis 10, wenn Z eine -NR15-Gruppe bedeutet, eine ganze Zahl von 2 bis 10, wenn Z -O-, D, E, F, und G -ob identisch oder unterschiedlich- je eine zweiwertige teerhaltige Gruppe mit 2 bis 6 Kohlenstoffatomen darstellen, f ist eine ganze Zahl von 1 bis 60, g und h - ob identisch oder unterschiedlich - bedeuten je Null oder eine ganze Zahl von 1 bis 50, und die Summe f + g + h ist eine ganze Zahl von 1 bis 60, wobei die für die Reaktion verwendete Polyaminmenge mindestens 0,1 Mol pro Mol des in die erste Phase eingebrachten Bernsteinsäurederivats beträgt.
  7. Formulierung gemäß einem der Ansprüche 1 bis 6, in der die Komponente (L) in der Gruppe der Produkteausgesucht wird, die aus der Reaktion in einer ersten Stufe von mindestens einem Bernsteinsäurederivat aus der Gruppe der Alkenylbernsteinsäureanhydride oder der Polyalkenylbernsteinsaureanhydride mit einer durchschnittlichen Molmasse von 200 bis 3 000 mit mindestens einem 1-(2-Hydroxyethyl-)imidazolin hervorgehen, das in der Position 2 der Gruppe des 1-(2-Hydroxethyl) -2-heptadecenylimdazolin und des 1-(2-Hydroxyethyl)-2-methylimidazolin substituiert wird; und in einer zweiten Stufe aus der Reaktion des aus der ersten Stufe stammenden Produktes mit mindestens einem Polyamin, das einer der folgenden Summenformeln entspricht:
    Figure 00410001
    Figure 00410002
    in denen Z eine NR15-Gruppe darstellt, R13, R14, R15 je ein Wasserstoffatom sind, a ist gleich 2 und b ist eine ganze Zahl von 1 bis 5, D, E, F, und G - ob identisch oder unterschiedlich - je eine Alkylengruppe mit 2 bis 4 Kohlenstoffatomen darstellen, f ist eine ganze Zahl von 1 bis 60, g und h bedeuten je Null oder f ist eine ganze Zahl von 1 bis 59, h ist gleich Null oder eine ganze Zahl, sodass die Summe f + h 1 bis 59 beträgt, und g ist eine ganze Zahl von 1 bis 50, wobei die Summe f + g + h in jedem Fall eine ganze Zahl von 1 bis 60 ist.
  8. Formulierung gemäß einem der Ansprüche 1 bis 7, in der die Komponente (L) in der Gruppe der Polyisobutene, der Polyisobutenamine, der Gemische aus diesen Verbindungsarten ausgesucht wird, vorzugsweise in Gemischen, die einen Minderanteil an Polyisobutenen und einen Hauptanteil an Polyisobuten-Ethylen-Diaminen enthalten.
  9. Formulierung gemäß einem der Ansprüche 1 bis 8, in der die Komponente (M) in der Gruppe der mineralischen oder synthetischen Schmieröle und der Polyglykole, die in dem besagten Treibstoff löslich sind und eine durchschnittliche Molmasse von 480 bis 2 100 aufweisen, ausgesucht wird, und folgende Summenformel hat (VII) :
    Figure 00420001
    in der jede einzelne R-Gruppe eine teerhaltige Gruppe mit 2 bis 6 Kohlenstoffatomen darstellt und x der durchschnittliche Polymerisationsgrad ist.
  10. Formulierung gemäß einem der Ansprüche 1 bis 9, in der die Komponente (M) ein Polyglykol mit einem Polydispersitätsgrad von 1 bis 1,25 mit der Summenformel (VIII) ist, in der jede einzelne R-Gruppe eine geradkettige oder verzweigte Alkylengruppe mit 2 bis 4 Kohlenstoffatomen, vorzugsweise eine Ethylen- oder eine Propylengruppe, darstellt.
  11. Formulierung gemäß einem der Ansprüche 1 bis 10, in der die Komponente (M) ein Polyglykol mit der Summenformel (VIII) ist, in der jede einzelne R-Gruppe eine Propylengruppe folgender Formel darstellt :
    Figure 00430001
    und a eine durchschnittliche Molmasse von 600 bis 1 800, vorzugsweise von 650 bis 1 250, aufweist.
  12. Verwendung einer Zusätzeformulierung nach einem der Ansprüche 1 bis 11 als Zusatz für einen Treibsoff, der auf Kohlenwasserstoffen oder auf einer Mischung von Kohlenwasser-stoffen und mindestens einer Sauerstoffverbindung basiert, die in der Alkohol- und Ethergruppe gewählt wird.
  13. Verwendung einer Zusätzeformulierung nach einem der Ansprüche 1 bis 11 als Zusatz für einen Treibstoff, der in Motoren mit gesteuerter Zündung verwenden wird.
  14. Verwendung nach Anspruch 12 oder 13, bei der der besagte Treibstoff von 10 bis 10 000 ppm der Zusätzeformulierung im Gewicht enthält.
  15. Verwendung nach Anspruch 14, bei der die Formulierung die Komponente (K), (L) und (M) in einem Gewichtsverhältnis [(K)/(L)] von 0,02 : 1 bis 4 : 1 und [(L)/(M)] in einem Gewichtsverhältnis von 0,05 : 1 bis 10 : 1 enthält.
  16. Heterocyclische Verbindung imidazo-oxazolischer Art, die eine alkoxylierte Seitenkette enthält und folgende Summenformel aufweist (I) :
    Figure 00440001
    in der R1 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 1 bis 40 Kohlenstoffatomen, R2 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 1 bis 12 Kohlenstoffatomen darstellt, wobei A, B, und C identisch oder unterschiedlich sind und jeweils eine zweiwertige teerhaltige Gruppe mit 2 bis 6 Kohlenstoffatomen darstellen, n ist eine ganze Zahl von 5 bis 50, m und p - ob identisch oder unterschiedlich - sind je gleich Null oder eine ganze Zahl von 1 bis 25, die Summe n + m + p ist eine ganze Zahl von 5 bis 50.
  17. Verbindung gemäß Anspruch 16 nach der Summenformel (I), in der R1 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 4 bis 25 Kohlenstoffatomen, R2 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 1 bis 6 Kohlenstoffatomen darstellt, wobei A, B, und C identisch oder unterschiedlich sind und jeweils eine zweiwertige teerhaltige Gruppe mit 2 bis 4 Kohlenstoffatomen darstellen, n ist eine ganze Zahl zwischen 10 und 50, m und p - ob identisch oder unterschiedlich - sind je gleich Null oder eine ganze Zahl von 1 bis 25, die Summe n + m + p ist eine ganze Zahl von 10 bis 50.
  18. Verbindung gemäß Anspruch 16 oder 17 nach der Summenformel (I), in der R1 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 4 bis 25 Kohlenstoffatomen, R2 ein Wasserstoffatom oder eine teerhaltige Gruppierung mit 1 bis 3 Kohlenstoffatomen darstellt, wobei A, B, und C identisch oder unterschiedlich sind und jeweils eine zweiwertige teerhaltige Gruppe mit 2 bis 4 Kohlenstoffatomen darstellen, n ist eine ganze Zahl zwischen 10 und 25, m und p - ob identisch oder unterschiedlich - sind je gleich Null oder eine ganze Zahl von 1 bis 25, die Summe n + m + p ist eine ganze Zahl von 10 bis 25.
  19. Verbindung gemäß einem der Ansprüche 16 bis 18 nach der Summenformel (I), in der R1 ein Wasserstoffatom oder eine Alkyl-, Alkenyl-, Aryl-, Alkaryl- oder Aralkylgruppierung, R2 ein Wasserstoffatom oder eine Alkylgruppierung, die geradkettig oder verzweigt, vorzugsweise geradkettig, ist, m und p sind gleich Null und A stellt die Dimethylengruppe, die Methyl-1 dimethylen-Gruppe oder die Ethyl-1 dimethylen-Gruppe dar.
  20. Verbindung gemäß einem der Ansprüche 16 bis 19 nach der Summenformel (I), in der R1 ein Wasserstoffatom oder eine Alkyl- oder eine Alkenylgruppierung, die geradkettig oder verzweigt ist, darstellt.
EP94401159A 1993-06-02 1994-05-25 Mindestens eine, alkoxylierte Imidazo-Oxazol Verbindung enthaltende Treibstoffzusätzeformulierung Expired - Lifetime EP0627483B1 (de)

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FR9306688A FR2705969B1 (fr) 1993-06-02 1993-06-02 Formulation d'additifs pour carburants comprenant au moins un composé imidazo-oxazole alkoxyle.
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FR2802207B1 (fr) * 1999-12-08 2002-01-18 Inst Francais Du Petrole Derives de l'isosorbide utilisables dans des compositions detergentes pour carburants de type essence
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US2987515A (en) * 1958-02-03 1961-06-06 Petrolite Corp Urethanes
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FR2486538A1 (fr) * 1980-07-08 1982-01-15 Inst Francais Du Petrole Compositions detergentes, leur preparation et leur utilisation comme additifs pour carburants
JPS5794069A (en) * 1980-12-02 1982-06-11 Canon Inc Recording liquid
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US4737160A (en) * 1984-11-02 1988-04-12 Phillips Petroleum Company Reaction products of amido-amine and epoxide useful as fuel additives
US4968321A (en) * 1989-02-06 1990-11-06 Texaco Inc. ORI-inhibited motor fuel composition
CA2020037A1 (en) * 1990-01-22 1991-07-23 Rodney L. Sung Polyoxyalkylene ester compounds and ori-inhibited motor fuel compositions
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FR2705969A1 (fr) 1994-12-09
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US5472457A (en) 1995-12-05
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